TW201942914A - Electrically conductive paste, electronic component, and laminated ceramic capacitor - Google Patents
Electrically conductive paste, electronic component, and laminated ceramic capacitor Download PDFInfo
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- 239000003985 ceramic capacitor Substances 0.000 title claims description 29
- 239000000843 powder Substances 0.000 claims abstract description 178
- 239000002270 dispersing agent Substances 0.000 claims abstract description 144
- 239000000919 ceramic Substances 0.000 claims abstract description 84
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- 239000002002 slurry Substances 0.000 claims description 48
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- 239000010408 film Substances 0.000 description 55
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
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- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 8
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- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 5
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- 229910052748 manganese Inorganic materials 0.000 description 2
- UODXCYZDMHPIJE-UHFFFAOYSA-N menthanol Chemical compound CC1CCC(C(C)(C)O)CC1 UODXCYZDMHPIJE-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 2
- 239000010944 silver (metal) Substances 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 2
- 239000011882 ultra-fine particle Substances 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- LAVARTIQQDZFNT-UHFFFAOYSA-N 1-(1-methoxypropan-2-yloxy)propan-2-yl acetate Chemical compound COCC(C)OCC(C)OC(C)=O LAVARTIQQDZFNT-UHFFFAOYSA-N 0.000 description 1
- HBNHCGDYYBMKJN-UHFFFAOYSA-N 2-(4-methylcyclohexyl)propan-2-yl acetate Chemical compound CC1CCC(C(C)(C)OC(C)=O)CC1 HBNHCGDYYBMKJN-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- WWJLCYHYLZZXBE-UHFFFAOYSA-N 5-chloro-1,3-dihydroindol-2-one Chemical compound ClC1=CC=C2NC(=O)CC2=C1 WWJLCYHYLZZXBE-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229920000896 Ethulose Polymers 0.000 description 1
- 239000001859 Ethyl hydroxyethyl cellulose Substances 0.000 description 1
- KGEKLUUHTZCSIP-UHFFFAOYSA-N Isobornyl acetate Natural products C1CC2(C)C(OC(=O)C)CC1C2(C)C KGEKLUUHTZCSIP-UHFFFAOYSA-N 0.000 description 1
- KRKIAJBQOUBNSE-GYSYKLTISA-N Isobornyl isobutyrate Chemical compound C1C[C@@]2(C)[C@H](OC(=O)C(C)C)C[C@@H]1C2(C)C KRKIAJBQOUBNSE-GYSYKLTISA-N 0.000 description 1
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 108010077895 Sarcosine Proteins 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000001940 [(1R,4S,6R)-1,7,7-trimethyl-6-bicyclo[2.2.1]heptanyl] acetate Substances 0.000 description 1
- FAFMZORPAAGQFV-BREBYQMCSA-N [(1r,3r,4r)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] propanoate Chemical compound C1C[C@@]2(C)[C@H](OC(=O)CC)C[C@@H]1C2(C)C FAFMZORPAAGQFV-BREBYQMCSA-N 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000004520 agglutination Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 235000019326 ethyl hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- DIICMQCJAQLQPI-UHFFFAOYSA-N isobornyl propionate Natural products CCC(=O)C1CC2CCC1(C)C2(C)C DIICMQCJAQLQPI-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229940079938 nitrocellulose Drugs 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 229940043230 sarcosine Drugs 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000005341 toughened glass Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/30—Stacked capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Ceramic Capacitors (AREA)
- Conductive Materials (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
Abstract
Description
本發明關於一種導電性漿料、電子零件以及層積陶瓷電容器。 The present invention relates to a conductive paste, an electronic component, and a laminated ceramic capacitor.
伴隨行動電話、數位設備等電子設備的小型化以及高性能化，對於包含層積陶瓷電容器等的電子零件亦期望小型化以及高容量化。層積陶瓷電容器具有將複數個電介質層及複數個內部電極層交替疊層而成的結構，藉由使前述電介質層以及內部電極層薄膜化而能夠實現小型化以及高容量化。 Along with miniaturization and high performance of electronic devices such as mobile phones and digital devices, miniaturization and high capacity of electronic components including laminated ceramic capacitors are also desired. A multilayer ceramic capacitor has a structure in which a plurality of dielectric layers and a plurality of internal electrode layers are alternately laminated. By reducing the thickness of the dielectric layer and the internal electrode layer, miniaturization and high capacity can be achieved.
例如，可藉由如下方式來製造層積陶瓷電容器。首先，在含有鈦酸鋇(BaTiO3)等電介質粉末以及黏合劑樹脂的電介質生片的表面上，以規定的電極圖案印刷(塗佈)內部電極用的導電性漿料，並進行乾燥而形成乾燥膜。接著，以使乾燥膜及電介質生片交替地重疊的方式進行層疊，進行加熱壓接而使其一體化，從而形成壓接體。將該壓接體切斷，在氧化性氣體環境或惰性氣體環境中進行脫有機黏合劑處理之後進行燒製，得到燒製晶片(層積體)。接著，在燒製晶片(層積體)的兩端部塗佈外部電極用漿料，在燒製後，在外部電極表面實施鍍鎳等，從而得到層 積陶瓷電容器。 For example, a laminated ceramic capacitor can be manufactured as follows. First, a conductive paste for internal electrodes is printed (coated) with a predetermined electrode pattern on the surface of a dielectric green sheet containing a dielectric powder such as barium titanate (BaTiO 3 ) and a binder resin, and dried to form Dry the film. Next, the dry film and the dielectric green sheet are laminated alternately, and are heat-pressed and integrated to form a pressure-bonded body. This pressure-bonded body is cut, and the organic binder is removed in an oxidizing gas atmosphere or an inert gas atmosphere, followed by firing to obtain a fired wafer (layered body). Next, a slurry for external electrodes is applied to both ends of the fired wafer (layered body), and after firing, nickel plating or the like is performed on the surface of the external electrode to obtain a laminated ceramic capacitor.
一般而言，用於形成內部電極的導電性漿料含有導電性粉末、陶瓷粉末、黏合劑樹脂以及有機溶劑。另外，為了提高導電性粉末等的分散性，導電性漿料有時含有分散劑。伴隨近年來的內部電極層的薄膜化，導電性粉末亦存在小粒徑化的傾向。在導電性粉末的粒徑較小的情況下，其顆粒表面的比表面積變大，因此導電性粉末(金屬粉末)的表面活性變高，存在分散性降低、黏度特性降低的情況。 Generally, a conductive paste for forming an internal electrode contains a conductive powder, a ceramic powder, a binder resin, and an organic solvent. In order to improve the dispersibility of the conductive powder and the like, the conductive paste may contain a dispersant. With the recent reduction in the thickness of the internal electrode layer, the conductive powder tends to have a smaller particle size. When the particle size of the conductive powder is small, the specific surface area of the particle surface becomes large, so the surface activity of the conductive powder (metal powder) becomes high, and the dispersibility and viscosity characteristics may be lowered.
因此，嘗試對導電性漿料的隨時間的黏度特性進行改善。例如，在專利文獻1中記載一種導電性漿料，其至少含有金屬成分、氧化物、分散劑及黏合劑樹脂，金屬成分係其表面組成具有特定的組成比的Ni粉末，分散劑的酸點量為500~2000μmol/g，黏合劑樹脂的酸點量為15~100μmol/g。而且，根據專利文獻1，該導電性漿料具有良好的分散性及黏度穩定性。 Therefore, attempts have been made to improve the viscosity characteristics of the conductive paste over time. For example, Patent Literature 1 describes a conductive paste containing at least a metal component, an oxide, a dispersant, and a binder resin. The metal component is a Ni powder whose surface composition has a specific composition ratio, and an acid point of the dispersant. The amount is 500 to 2000 μmol / g, and the acid point amount of the binder resin is 15 to 100 μmol / g. Furthermore, according to Patent Document 1, the conductive paste has good dispersibility and viscosity stability.
另外，在專利文獻2中記載一種內部電極用導電性漿料，其由導電性粉末、樹脂、有機溶劑、以BaTiO3為主的陶瓷粉末的共材以及凝集抑制劑構成，其中，前述凝集抑制劑的含量為0.1重量%以上5重量%以下，前述凝集抑制劑係以特定的結構式表示的叔胺或仲胺。根據專利文獻2，該內部電極用導電漿料抑制共材成分的凝集，長期保管性優異，能夠實現層疊陶瓷電容器的薄膜化。 In addition, Patent Document 2 describes a conductive paste for internal electrodes, which is composed of a common material of a conductive powder, a resin, an organic solvent, a ceramic powder mainly composed of BaTiO 3 , and an aggregation inhibitor. The content of the agent is 0.1% by weight or more and 5% by weight or less. The agglutination inhibitor is a tertiary or secondary amine represented by a specific structural formula. According to Patent Document 2, this conductive paste for internal electrodes suppresses agglomeration of a common material component, is excellent in long-term storage, and can realize a thin film of a multilayer ceramic capacitor.
另一方面，在使內部電極層薄膜化時，要求藉由在電介質生片表面上印刷導電性漿料並乾燥而得到的乾燥膜具有較高的密度。例如，在專利文獻3中提出一種金屬超微粉漿料，其含有有機溶劑、表面活 性劑以及金屬超微顆粒，其中，前述表面活性劑為油醯肌胺酸，在前述金屬超微粉漿料中，含有70質量%以上95質量%以下的前述金屬超微粉，以前述金屬超微粉為100質量份計，含有超過0.05質量份且不足2.0質量份的前述表面活性劑。根據專利文獻3，藉由防止超微顆粒的凝集，能夠得到不存在凝聚顆粒的、分散性以及乾燥膜密度優異的金屬超微粉漿料。 On the other hand, when the internal electrode layer is formed into a thin film, a dried film obtained by printing a conductive paste on the surface of a dielectric green sheet and drying the film is required to have a high density. For example, Patent Document 3 proposes a metal ultrafine powder slurry containing an organic solvent, a surfactant, and metal ultrafine particles, wherein the surfactant is oleosine sarcosine, and the metal ultrafine powder slurry It contains 70% by mass or more and 95% by mass or less of the aforementioned metal ultrafine powder. Based on 100 parts by mass of the aforementioned metal ultrafine powder, it contains more than 0.05 parts by mass and less than 2.0 parts by mass of the aforementioned surfactant. According to Patent Document 3, by preventing aggregation of ultrafine particles, a metal ultrafine powder slurry having excellent dispersibility and dry film density without agglomerated particles can be obtained.
專利文獻1：日本特開2015-216244號公報 Patent Document 1: Japanese Patent Application Laid-Open No. 2015-216244
專利文獻2：日本特開2013-149457號公報 Patent Document 2: Japanese Patent Application Laid-Open No. 2013-149457
專利文獻3：日本特開2006-063441號公報 Patent Document 3: Japanese Patent Application Laid-Open No. 2006-063441
隨著近年來的電極圖案、電介質層的薄膜化，為了高精度地維持各電極圖案之間的間隙，要求不存在因導電性粉末凝集而成的粗大顆粒引起的表面粗糙等的更加平滑的電極表面。 With the recent reduction in the thickness of electrode patterns and dielectric layers, in order to maintain the gap between the electrode patterns with high accuracy, smoother electrodes, such as surface roughness caused by coarse particles formed by the aggregation of conductive powder, are required. surface.
有鑒於此，本發明的目的在於提供一種進一步提高導電性粉末以及陶瓷粉末的分散性的導電性漿料。 In view of this, an object of the present invention is to provide a conductive paste that further improves the dispersibility of conductive powder and ceramic powder.
本發明的第一態樣提供一種導電性漿料，其含有導電性粉 末、陶瓷粉末、分散劑、黏合劑樹脂以及有機溶劑；分散劑含有酸系分散劑；酸系分散劑的平均分子量超過500且為2000以下，並且，相對於主鏈，具有一個以上的由烴基構成的支鏈。 A first aspect of the present invention provides a conductive paste containing a conductive powder, ceramic powder, a dispersant, a binder resin, and an organic solvent; the dispersant contains an acid-based dispersant; and the average molecular weight of the acid-based dispersant exceeds 500 It is 2000 or less, and has one or more branched chains composed of a hydrocarbon group with respect to the main chain.
另外，酸系分散劑理想為具有羧基的酸系分散劑，更理想為以聚羧酸為主鏈的烴系接枝共聚物。另外，以導電性粉末為100質量份計，理想為含有0.01質量份以上5質量份以下的酸系分散劑。另外，分散劑亦可進一步含有鹼系分散劑。另外，鹼系分散劑理想為選自脂肪族胺或聚醚胺中的一種或兩種的混合。另外，以導電性粉末為100質量份計，理想為含有0.01質量份以上3質量份以下的鹼系分散劑。另外，導電性粉末理想為含有選自Ni、Pd、Pt、Au、Ag、Cu以及其等的合金中的至少一種的金屬粉末。另外，導電性粉末的平均粒徑理想為0.05μm以上1.0μm以下。另外，陶瓷粉末理想為含有鈣鈦礦型氧化物。另外，陶瓷粉末的平均粒徑理想為0.01μm以上0.5μm以下。另外，黏合劑樹脂理想為含有纖維素系樹脂、丙烯酸系樹脂以及丁醛系樹脂中的至少一種。另外，在上述導電性漿料理想為用於層積陶瓷零件的內部電極。 The acid-based dispersant is preferably an acid-based dispersant having a carboxyl group, and more preferably a hydrocarbon-based graft copolymer having a polycarboxylic acid as a main chain. The conductive powder is preferably contained in an amount of 0.01 to 5 parts by mass based on 100 parts by mass of the acid-based dispersant. The dispersant may further contain an alkali-based dispersant. The alkali-based dispersant is preferably a mixture of one or two selected from aliphatic amines and polyetheramines. The conductive powder is preferably contained in an amount of 0.01 parts by mass or more and 3 parts by mass or less based on 100 parts by mass of the conductive powder. The conductive powder is preferably a metal powder containing at least one selected from the group consisting of Ni, Pd, Pt, Au, Ag, Cu, and alloys thereof. The average particle diameter of the conductive powder is preferably from 0.05 μm to 1.0 μm. The ceramic powder preferably contains a perovskite-type oxide. The average particle diameter of the ceramic powder is preferably from 0.01 μm to 0.5 μm. The binder resin preferably contains at least one of a cellulose-based resin, an acrylic resin, and a butyraldehyde-based resin. The conductive paste is preferably used as an internal electrode for laminated ceramic parts.
本發明的第二態樣提供一種使用上述導電性漿料而形成的電子零件。 According to a second aspect of the present invention, there is provided an electronic component formed using the conductive paste.
本發明的第三態樣提供一種層積陶瓷電容器，其至少具有將電介質層及內部電極進行層疊而成的層積體，前述內部電極使用上述導電性漿料而形成。 According to a third aspect of the present invention, there is provided a laminated ceramic capacitor including at least a laminated body in which a dielectric layer and an internal electrode are laminated, and the internal electrode is formed using the conductive paste.
根據本發明的導電性漿料，可提高作為粉末材料的導電性粉末、陶瓷粉末的分散性，並且，可提高塗佈後的乾燥電極表面的平滑性。另外，作為使用本發明的導電性漿料而形成的層積陶瓷電容器等電子零件的電極圖案，即使於形成薄膜化的電極時，導電性漿料的印刷性亦很優異，能夠具有高精度且均勻的寬度以及厚度。 According to the conductive paste of the present invention, the dispersibility of the conductive powder and the ceramic powder as a powder material can be improved, and the smoothness of the surface of the dried electrode after coating can be improved. In addition, as an electrode pattern of an electronic component such as a laminated ceramic capacitor formed using the conductive paste of the present invention, even when a thin-film electrode is formed, the conductive paste has excellent printability and can have high accuracy and high accuracy. Uniform width and thickness.
1‧‧‧層積陶瓷電容器 1‧‧‧Laminated ceramic capacitors
10‧‧‧陶瓷層積體 10‧‧‧Ceramic laminate
11‧‧‧內部電極層 11‧‧‧Internal electrode layer
12‧‧‧電介質層 12‧‧‧ Dielectric layer
20‧‧‧外部電極 20‧‧‧External electrode
21‧‧‧外部電極層 21‧‧‧External electrode layer
22‧‧‧電鍍層 22‧‧‧Plating
【圖1】係表示實施型態所關於之層積陶瓷電容器的立體圖以及剖視圖。 Fig. 1 is a perspective view and a cross-sectional view showing a multilayer ceramic capacitor according to an embodiment.
本實施型態的導電性漿料含有導電性粉末、陶瓷粉末、分散劑、黏合劑樹脂以及有機溶劑。以下，對各成分進行詳細說明。 The conductive paste according to the embodiment includes a conductive powder, a ceramic powder, a dispersant, a binder resin, and an organic solvent. Hereinafter, each component is demonstrated in detail.
(導電性粉末) (Conductive powder)
對導電性粉末無特別限定，可使用習知的金屬粉末。導電性粉末例如可使用選自Ni、Pd、Pt、Au、Ag、Cu以及其等的合金的一種以上的粉末。其中，以導電性、耐腐蝕性以及成本的觀點而言，理想為Ni或其合金的粉末(以下，亦稱為「Ni粉末」)。作為Ni合金，例如可使用選自Mn、Cr、Co、Al、Fe、Cu、Zn、Ag、Au、Pt以及Pd所成群中的至少一種以上的元素與Ni的合金。Ni合金中的Ni的含量例如為50質量%以上，理想為80質量%以上。另外，為了抑制脫黏合劑處理時的、由黏合劑 樹脂的部分的熱分解而導致的劇烈的氣體產生，Ni粉末可含有幾百ppm程度的元素S。 The conductive powder is not particularly limited, and a conventional metal powder can be used. As the conductive powder, for example, one or more kinds of powders selected from Ni, Pd, Pt, Au, Ag, Cu, and alloys thereof can be used. Among these, from the viewpoints of conductivity, corrosion resistance, and cost, powders of Ni or an alloy thereof (hereinafter, also referred to as “Ni powders”) are preferred. As the Ni alloy, for example, an alloy of at least one or more elements selected from the group consisting of Mn, Cr, Co, Al, Fe, Cu, Zn, Ag, Au, Pt, and Pd, and Ni can be used. The content of Ni in the Ni alloy is, for example, 50% by mass or more, and preferably 80% by mass or more. In addition, in order to suppress severe gas generation due to thermal decomposition of a part of the binder resin during debinder treatment, the Ni powder may contain element S of several hundred ppm.
導電性粉末的平均粒徑理想為0.05μm以上1.0μm以下，更理想為0.1μm以上0.5μm以下。在導電性粉末的平均粒徑為上述範圍內的情況下，能夠適宜用作薄膜化的層積陶瓷電容器(層積陶瓷零件)的內部電極用漿料，例如，可提高乾燥膜的平滑性以及乾燥膜密度。平均粒徑係根據基於掃描型電子顯微鏡(SEM)的觀察而求出的值，係從藉由SEM以10,000倍的倍率進行觀察而得到的圖像中逐個測定複數個顆粒的粒徑而得到的個數平均值。 The average particle diameter of the conductive powder is preferably from 0.05 μm to 1.0 μm, and more preferably from 0.1 μm to 0.5 μm. When the average particle diameter of the conductive powder is within the above range, it can be suitably used as a slurry for internal electrodes of a thin-film laminated ceramic capacitor (multilayer ceramic parts). For example, it can improve the smoothness of a dried film and Dry film density. The average particle diameter is a value obtained by observation with a scanning electron microscope (SEM), and is obtained by measuring the particle diameter of a plurality of particles one by one from an image obtained by observation with a SEM at a magnification of 10,000 times. Number average.
導電性粉末的含量相對於導電性漿料整體理想為30質量%以上且不足70質量%，更理想為40質量%以上60質量%以下。在導電性粉末的含量為上述範圍內的情況下，導電性以及分散性優異。 The content of the conductive powder is preferably 30% by mass or more and less than 70% by mass, and more preferably 40% by mass or more and 60% by mass or less with respect to the entire conductive paste. When the content of the conductive powder is within the above range, the conductivity and dispersibility are excellent.
(陶瓷粉末) (Ceramic powder)
作為陶瓷粉末，無特別限定，例如，在用於層積陶瓷電容器的內部電極用漿料的情況下，可根據所應用的層積陶瓷電容器的種類而適當地選擇習知的陶瓷粉末。作為陶瓷粉末，例如可列舉為含有Ba以及Ti的鈣鈦礦型氧化物，理想為鈦酸鋇(BaTiO3)。 The ceramic powder is not particularly limited. For example, in the case of a slurry for internal electrodes of a laminated ceramic capacitor, a conventional ceramic powder can be appropriately selected according to the type of the laminated ceramic capacitor to be applied. Examples of the ceramic powder include a perovskite-type oxide containing Ba and Ti, and preferably barium titanate (BaTiO 3 ).
作為陶瓷粉末，可使用含有鈦酸鋇作為主成分、且含有氧化物作為副成分的陶瓷粉末。作為氧化物，可列舉為選自Mn、Cr、Si、Ca、Ba、Mg、V、W、Ta、Nb以及稀土類元素中的一種以上所構成的氧化物。 As the ceramic powder, a ceramic powder containing barium titanate as a main component and an oxide as a subcomponent can be used. Examples of the oxide include oxides composed of one or more selected from the group consisting of Mn, Cr, Si, Ca, Ba, Mg, V, W, Ta, Nb, and rare earth elements.
另外，作為陶瓷粉末，例如可使用將鈦酸鋇(BaTiO3)的 Ba原子、Ti原子以例如Sn、Pb、Zr等其他原子取代後的鈣鈦礦型氧化物強電介質的陶瓷粉末。 In addition, as the ceramic powder, for example, a ceramic powder of a perovskite-type oxide ferroelectric in which Ba atoms and Ti atoms of barium titanate (BaTiO 3 ) are replaced with other atoms such as Sn, Pb, and Zr can be used.
在作為內部電極用漿料使用的情況下，陶瓷粉末可使用與構成層積陶瓷電容器(電子零件)的電介質生片的電介質陶瓷粉末相同組成的粉末。藉此，可抑制由於燒結工序中的電介質層與內部電極層之間的界面處的收縮失配而導致的裂紋的產生。作為如此之陶瓷粉末，除上述含有Ba以及Ti的鈣鈦礦型氧化物以外，例如，亦可列舉為ZnO、鐵氧體、PZT、BaO、Al2O3、Bi2O3、R(稀土類元素)2O3、TiO2、Nd2O3等氧化物。此外，陶瓷粉末可使用一種，亦可使用兩種以上。 When used as a slurry for internal electrodes, the ceramic powder may be a powder having the same composition as a dielectric ceramic powder constituting a dielectric green sheet of a laminated ceramic capacitor (electronic component). Thereby, generation of cracks due to shrinkage mismatch at the interface between the dielectric layer and the internal electrode layer in the sintering process can be suppressed. As such a ceramic powder, in addition to the above-mentioned perovskite-type oxides containing Ba and Ti, for example, ZnO, ferrite, PZT, BaO, Al 2 O 3 , Bi 2 O 3 , R (rare earth) Element-like) 2 O 3 , TiO 2 , Nd 2 O 3 and other oxides. In addition, one type of ceramic powder may be used, or two or more types may be used.
陶瓷粉末的平均粒徑例如為0.01μm以上0.5μm以下，理想為0.01μm以上0.3μm以下的範圍。藉由使陶瓷粉末的平均粒徑在上述範圍內，在作為內部電極用漿料來使用的情況下，能夠形成足夠細薄且均勻的內部電極。平均粒徑係根據基於掃描型電子顯微鏡(SEM)的觀察而求出的值，係從藉由SEM以50,000倍的倍率進行觀察而得到的影像中逐個測定複數個顆粒的粒徑而得到的個數平均值。 The average particle diameter of the ceramic powder is, for example, from 0.01 μm to 0.5 μm, and preferably from 0.01 μm to 0.3 μm. When the average particle diameter of the ceramic powder is within the above range, when it is used as a slurry for internal electrodes, a sufficiently thin and uniform internal electrode can be formed. The average particle diameter is a value obtained by observation with a scanning electron microscope (SEM), and is obtained by measuring the particle diameter of a plurality of particles one by one from an image obtained by observation with a SEM at a magnification of 50,000 times. Number average.
以導電性粉末為100質量份計，陶瓷粉末的含量理想為1質量份以上30質量份以下，更理想為3質量份以上30質量份以下。 The content of the ceramic powder is preferably 1 part by mass or more and 30 parts by mass or less based on 100 parts by mass of the conductive powder, and more preferably 3 parts by mass or more and 30 parts by mass or less.
陶瓷粉末的含量相對於導電性漿料整體理想為1質量%以上20質量%以下，更理想為3質量%以上20質量%以下。 The content of the ceramic powder is preferably 1% by mass or more and 20% by mass or less, and more preferably 3% by mass or more and 20% by mass or less with respect to the entire conductive paste.
(黏合劑樹脂) (Binder resin)
作為黏合劑樹脂，無特別限定，可使用習知的樹脂。作為黏合劑樹脂，例如可列舉為甲基纖維素、乙基纖維素、乙基羥基乙基纖維素、硝基 纖維素等纖維素系樹脂、丙烯酸系樹脂、聚乙烯醇縮丁醛等丁醛系樹脂等。其中，以相對於溶劑的溶解性、燃燒分解性的觀點等而言，理想為含有乙基纖維素。另外，在用於內部電極用漿料的情況下，以提高與電介質生片之間的黏合強度的觀點而言，可含有丁醛系樹脂，或者可單獨使用丁醛系樹脂。黏合劑樹脂可使用一種，或者亦可使用兩種以上。另外，以改善各種特性的觀點而言，黏合劑樹脂理想為使用纖維素系樹脂及丁醛系樹脂的混合物。另外，黏合劑樹脂的分子量例如為20000~200000左右。 The binder resin is not particularly limited, and a known resin can be used. Examples of the binder resin include cellulose resins such as methyl cellulose, ethyl cellulose, ethyl hydroxyethyl cellulose, and nitro cellulose, butyraldehyde such as acrylic resin, and polyvinyl butyral. Department of resin and so on. Among these, ethyl cellulose is preferably contained from the viewpoints of solubility in a solvent, combustion decomposition properties, and the like. Moreover, when using for the slurry for internal electrodes, a butyraldehyde-based resin may be contained from the viewpoint of improving the adhesive strength with a dielectric green sheet, or a butyraldehyde-based resin may be used alone. One kind of binder resin may be used, or two or more kinds may be used. From the viewpoint of improving various characteristics, the binder resin is preferably a mixture of a cellulose-based resin and a butyraldehyde-based resin. The molecular weight of the binder resin is, for example, about 20,000 to 200,000.
以導電性粉末為100質量份計，黏合劑樹脂的含量理想為1質量份以上20質量份以下，更理想為1質量份以上15質量份以下。 The content of the binder resin is preferably 1 part by mass or more and 20 parts by mass or less based on 100 parts by mass of the conductive powder, and more preferably 1 part by mass or more and 15 parts by mass or less.
黏合劑樹脂的含量相對於導電性漿料整體理想為0.5質量%以上10質量%以下，更理想為1質量%以上6質量%以下。在黏合劑樹脂的含量為上述範圍內的情況下，導電性以及分散性優異。 The content of the binder resin is preferably 0.5 mass% or more and 10 mass% or less, and more preferably 1 mass% or more and 6 mass% or less with respect to the entire conductive paste. When the content of the binder resin is within the above range, the conductivity and dispersibility are excellent.
(有機溶劑) (Organic solvents)
作為有機溶劑，無特別限定，可使用能夠溶解上述黏合劑樹脂的習知的有機溶劑。作為有機溶劑，例如可列舉為二氫萜品醇乙酸酯、乙酸異冰片酯、丙酸異冰片酯、丁酸異冰片酯以及異丁酸異冰片酯、乙二醇單丁醚乙酸酯、二丙二醇甲基醚乙酸酯等乙酸酯系溶劑、萜品醇、二氫萜品醇等萜系溶劑、十三烷、壬烷、環己烷等烴系溶劑等。其中，理想為使用萜品醇等萜系溶劑。此外，有機溶劑可使用一種，亦可使用兩種以上。 The organic solvent is not particularly limited, and a conventional organic solvent capable of dissolving the above-mentioned binder resin can be used. Examples of the organic solvent include dihydroterpineol acetate, isobornyl acetate, isobornyl propionate, isobornyl butyrate, isobornyl isobutyrate, and ethylene glycol monobutyl ether acetate. , Acetate solvents such as dipropylene glycol methyl ether acetate, terpenoid solvents such as terpineol and dihydroterpineol, hydrocarbon solvents such as tridecane, nonane, and cyclohexane. Among them, terpene-based solvents such as terpineol are preferably used. In addition, one type of organic solvent may be used, or two or more types may be used.
以導電性粉末為100質量份計，有機溶劑的含量理想為40質量份以上100質量份以下，更理想為65質量份以上95質量份以下。在有機溶劑的含量為上述範圍內的情況下，導電性以及分散性優異。 The content of the organic solvent is preferably 40 parts by mass or more and 100 parts by mass or less based on 100 parts by mass of the conductive powder, and more preferably 65 parts by mass or more and 95 parts by mass or less. When the content of the organic solvent is within the above range, the conductivity and dispersibility are excellent.
有機溶劑的含量相對於導電性漿料整體理想為20質量%以上60質量%以下，更理想為35質量%以上55質量%以下。在有機溶劑的含量為上述範圍內的情況下，導電性以及分散性優異。 The content of the organic solvent is preferably 20% by mass or more and 60% by mass or less, and more preferably 35% by mass or more and 55% by mass or less with respect to the entire conductive paste. When the content of the organic solvent is within the above range, the conductivity and dispersibility are excellent.
(分散劑) (Dispersant)
本發明的發明人針對在導電性漿料中使用的分散劑對各種分散劑進行研究的結果為，發現：藉由使用平均分子量超過500且為2000以下、並且相對於主鏈而具有一個以上的由烴基構成的支鏈的酸系分散劑，能夠提高導電性漿料中含有的粉末材料(導電性粉末以及陶瓷粉末)的分散性，並且，能夠提高乾燥膜表面的平滑性。其理由的詳情雖然不明，但考慮係由於酸系分散劑具有由烴基構成的支鏈，從而有效地形成立體位阻而抑制粉末材料的凝集，並且藉由設為特定大小的分子量，從而能夠維持適於導電性漿料的黏度。以下，對本實施型態中使用的酸系分散劑進一步詳細地進行說明。 The inventors of the present invention studied various dispersants with respect to the dispersant used in the conductive paste, and found that by using an average molecular weight of more than 500 to 2000 or less and having one or more The branched acid-based dispersant composed of a hydrocarbon group can improve the dispersibility of the powder material (conductive powder and ceramic powder) contained in the conductive paste, and can improve the smoothness of the surface of the dried film. Although the details of the reason are unknown, it is considered that the acid-based dispersant has branched chains composed of hydrocarbon groups, thereby effectively forming steric hindrance and suppressing aggregation of the powder material. By setting the molecular weight to a specific size, it can maintain an appropriate On the viscosity of conductive paste. Hereinafter, the acid-based dispersant used in this embodiment will be described in more detail.
酸系分散劑相對於主鏈而具有一個以上的由烴基構成的支鏈，理想為具有複數個。另外，酸系分散劑理想為具有羧基，更理想為以聚羧酸為主鏈的徑系接枝共聚物。 The acid-based dispersant preferably has one or more branched chains composed of a hydrocarbon group with respect to the main chain, and preferably has a plurality of them. The acid-based dispersant preferably has a carboxyl group, and more preferably a radial graft copolymer having a polycarboxylic acid as a main chain.
酸系分散劑的分子量超過500且為2000以下。當分子量在上述範圍內的情況下，導電性粉末以及陶瓷粉末的分散性優異，乾燥膜表面的密度以及平滑性優異。 The molecular weight of the acid-based dispersant exceeds 500 and is 2,000 or less. When the molecular weight is within the above range, the dispersibility of the conductive powder and the ceramic powder is excellent, and the density and smoothness of the surface of the dried film are excellent.
就酸系分散劑而言，例如可從市售的產品中選擇滿足上述特性的酸系分散劑來使用。另外，就酸系分散劑而言，亦可使用以往習知的製造方法來製造以滿足上述特性。 As the acid-based dispersant, for example, an acid-based dispersant that satisfies the above characteristics can be selected from commercially available products and used. The acid-based dispersant can also be produced using a conventionally known production method to satisfy the aforementioned characteristics.
以導電性粉末為100質量份計，理想為含有0.01質量份以上5質量份以下的酸系分散劑，更理想為含有0.05質量份以上3質量份以下。在酸系分散劑的含量為上述範圍內的情況下，導電性粉末以及陶瓷粉末的分散性、乾燥膜表面的平滑性更加優異。另外，能夠將導電性漿料的黏度調整至適當的範圍，並且能夠抑制片材侵蝕、生片的剝離不良。 The conductive powder is preferably contained in an amount of 0.01 parts by mass or more and 5 parts by mass or less based on 100 parts by mass of the conductive powder, and more preferably 0.05 parts by mass or more and 3 parts by mass or less. When the content of the acid-based dispersant is within the above range, the dispersibility of the conductive powder and the ceramic powder and the smoothness of the surface of the dried film are more excellent. In addition, the viscosity of the conductive paste can be adjusted to an appropriate range, and sheet erosion and peeling failure of the green sheet can be suppressed.
另外，以導電性粉末為100質量份計，酸系分散劑的含量的下限可超過0.1質量份，亦可超過0.5質量份。在酸系分散劑的含量的下限為上述範圍內的情況下，導電性粉末以及陶瓷粉末的分散性、乾燥膜表面的平滑性更加優異。 In addition, based on 100 parts by mass of the conductive powder, the lower limit of the content of the acid-based dispersant may exceed 0.1 parts by mass, and may also exceed 0.5 parts by mass. When the lower limit of the content of the acid-based dispersant is within the above range, the dispersibility of the conductive powder and the ceramic powder and the smoothness of the surface of the dried film are more excellent.
另外，以導電性粉末為100質量份計，酸系分散劑的含量的上限可為1.5質量份以下，亦可為1質量份以下。在酸系分散劑的含量的上限為上述範圍內的情況下，導電性粉末以及陶瓷粉末的分散性、乾燥膜表面的平滑性亦足夠優異，並且，能夠抑制片材侵蝕、生片的剝離不良。 In addition, the upper limit of the content of the acid-based dispersant may be 1.5 parts by mass or less, and may be 1 part by mass or less based on 100 parts by mass of the conductive powder. When the upper limit of the content of the acid-based dispersant is within the above range, the dispersibility of the conductive powder and the ceramic powder and the smoothness of the surface of the dried film are also sufficiently excellent, and sheet erosion and peeling failure of the green sheet can be suppressed. .
另外，相對於導電性漿料總量，理想為含有3質量%以下的酸系分散劑。酸系分散劑的含量的上限理想為2質量%以下，更理想為1質量%以下。酸系分散劑的含量的下限無特別限定，例如為0.01質量%以上，理想為0.05質量%以上。在酸系分散劑的含量為上述範圍內的情況下，能夠將導電性漿料的黏度調整至適當的範圍，並且能夠抑制片材侵蝕、生片的剝離不良。 The acid-based dispersant is preferably contained in an amount of 3% by mass or less based on the total amount of the conductive paste. The upper limit of the content of the acid-based dispersant is preferably 2% by mass or less, and more preferably 1% by mass or less. The lower limit of the content of the acid-based dispersant is not particularly limited, and is, for example, 0.01% by mass or more, and preferably 0.05% by mass or more. When the content of the acid-based dispersant is within the above range, the viscosity of the conductive paste can be adjusted to an appropriate range, and sheet erosion and peeling failure of the green sheet can be suppressed.
本實施型態所關於之導電性漿料中，作為分散劑，可進一步含有鹼系分散劑。對鹼系分散劑的種類無特別限定，其中更理想為選自 脂肪族胺以及聚醚胺中的一種或兩種以上。 The conductive paste according to the embodiment may further contain an alkali-based dispersant as a dispersant. The type of the alkali-based dispersant is not particularly limited, and among them, one or two or more kinds selected from aliphatic amines and polyetheramines are more preferable.
以導電性粉末為100質量份計，理想為含有0.01質量份以上3質量份以下的鹼系分散劑，更理想為含有0.01質量份以上1質量份以下，進一步理想為含有0.05質量份以上1質量份以下。在鹼系分散劑的含量為上述範圍內的情況下，能夠將導電性漿料的黏度調整至適當的範圍，並且能夠進一步提高導電性粉末、陶瓷粉末的分散性、乾燥膜表面的平滑性。另外，能夠進一步抑制片材侵蝕、生片的剝離不良。 Based on 100 parts by mass of the conductive powder, it is desirable to contain 0.01 to 3 parts by mass of an alkali-based dispersant, more preferably to contain 0.01 to 1 part by mass, and even more preferred to contain 0.05 to 1 part by mass. The following. When the content of the alkali-based dispersant is within the above range, the viscosity of the conductive paste can be adjusted to an appropriate range, and the dispersibility of the conductive powder and ceramic powder, and the smoothness of the surface of the dried film can be further improved. In addition, sheet erosion and peeling failure of the green sheet can be further suppressed.
另外，例如，以導電性粉末為100質量份計，即使在含有1質量份以下的酸系分散劑的情況下，藉由含有0.01質量份以上0.3質量份以下、理想為含有0.01質量份以上0.2質量份以下的鹼系分散劑，亦能夠使得導電性粉末、陶瓷粉末的分散性以及乾燥膜的平滑性優異，並且將導電性漿料的黏度調整至適當的範圍。 In addition, for example, when the conductive powder is 100 parts by mass, even when the acid-based dispersant is contained in an amount of 1 part by mass or less, the content is preferably 0.01 part by mass or more and 0.3 part by mass or less, preferably 0.01 part by mass or more and 0.2. Alkali-based dispersants in parts by mass or less can also make conductive powders and ceramic powders excellent in dispersibility and dry film smoothness, and can adjust the viscosity of the conductive paste to an appropriate range.
另外，相對於導電性漿料整體，理想為含有2質量%以下的鹼系分散劑。鹼系分散劑的含量的上限理想為1.5質量%以下，更理想為1質量%以下。另外，鹼系分散劑的含量的上限可為0.5質量%以下，亦可為0.2質量%以下。另外，鹼系分散劑的含量的下限無特別限定，例如為0.01質量%以上，理想為0.02質量%以上，亦可為0.05質量%以上。在鹼系分散劑的含量為上述範圍內的情況下，能夠將導電性漿料的黏度調整至適當的範圍，並且能夠進一步提高導電性粉末、陶瓷粉末的分散性、塗佈後的乾燥電極表面的平滑性。另外，能夠進一步抑制片材侵蝕、生片的剝離不良。 In addition, it is desirable to contain an alkali-based dispersant in an amount of 2% by mass or less with respect to the entire conductive paste. The upper limit of the content of the alkali-based dispersant is preferably 1.5% by mass or less, and more preferably 1% by mass or less. The upper limit of the content of the alkali-based dispersant may be 0.5% by mass or less, and may also be 0.2% by mass or less. The lower limit of the content of the alkali-based dispersant is not particularly limited, and is, for example, 0.01% by mass or more, preferably 0.02% by mass or more, and may be 0.05% by mass or more. When the content of the alkali-based dispersant is within the above range, the viscosity of the conductive paste can be adjusted to an appropriate range, and the dispersibility of the conductive powder and ceramic powder can be further improved, and the surface of the electrode after drying can be further improved Smoothness. In addition, sheet erosion and peeling failure of the green sheet can be further suppressed.
此外，導電性漿料可在不阻礙本發明的效果的範圍內含有 除上述酸系分散劑、鹼系分散劑以外的分散劑。作為上述以外的分散劑，例如可含有包含高級脂肪酸、高分子表面活性劑等的酸系分散劑、兩性表面活性劑以及高分子系分散劑等。另外，上述分散劑可一種或兩種以上組合使用。 The conductive paste may contain a dispersant other than the above-mentioned acid-based dispersant and alkali-based dispersant within a range that does not inhibit the effects of the present invention. Examples of the dispersant other than the above may include an acid-based dispersant containing a higher fatty acid, a polymer surfactant, and the like, an amphoteric surfactant, and a polymer-based dispersant. The dispersants may be used alone or in combination of two or more.
在含有上述酸系分散劑、鹼系分散劑以外的分散劑的情況下，以導電性粉末為100質量份計，分散劑總體的含量(總含量)理想為0.01質量份以上8質量份以下。另外，分散劑總體的含量(總含量)可為5質量份以下，亦可為3質量份以下，或者亦可為1質量份以下。在本實施型態所關於之導電性漿料中，藉由含有上述酸系分散劑，即使分散劑總體的含量在上述範圍內，亦能夠使分散性、平滑性、漿料黏度更加優異。 When the dispersant other than the acid-based dispersant and the alkali-based dispersant is contained, the content (total content) of the entire dispersant is preferably 0.01 parts by mass or more and 8 parts by mass or less based on 100 parts by mass of the conductive powder. The content (total content) of the entire dispersant may be 5 parts by mass or less, 3 parts by mass or less, or 1 part by mass or less. By including the above-mentioned acid-based dispersant in the conductive paste according to this embodiment, even if the total content of the dispersant is within the above range, dispersibility, smoothness, and slurry viscosity can be further improved.
(導電性漿料) (Conductive paste)
對本實施型態的導電性漿料的製造方法無特別限定，可使用以往習知的方法。例如，可藉由將上述各成分(導電性粉末、陶瓷粉末、分散劑、黏合劑樹脂、有機溶劑等)進行混合(攪拌、混煉)來製造導電性漿料。此外，在混合(攪拌、混煉)中使用的裝置無特別限定，例如可使用三輥磨、球磨機、混合機等。 The manufacturing method of the electrically conductive paste of this embodiment is not specifically limited, A conventionally well-known method can be used. For example, the conductive paste can be produced by mixing (stirring, kneading) the respective components (conductive powder, ceramic powder, dispersant, binder resin, organic solvent, etc.) described above. The device used for mixing (stirring, kneading) is not particularly limited, and for example, a three-roll mill, a ball mill, a mixer, or the like can be used.
上述各材料可同時混合，例如，可以在預先將導電性粉末、分散劑的一部分或者全部與有機溶劑的一部分混合而製備導電性粉末漿料之後將剩餘的材料混合。藉此，能夠預先在導電性粉末表面塗佈分散劑。若在導電性粉末的表面預先塗佈有分散劑，則在與其他材料進行混合來製造導電性漿料時，導電性粉末亦不會凝集而維持充分地分散的狀態，容易得到均勻的導電性漿料。 The above materials may be mixed at the same time. For example, a conductive powder, a part of the dispersant, or all of them may be mixed with a part of the organic solvent in advance to prepare a conductive powder slurry, and the remaining materials may be mixed. This makes it possible to apply a dispersant to the surface of the conductive powder in advance. If the surface of the conductive powder is coated with a dispersant in advance, the conductive powder will not aggregate and maintain a sufficiently dispersed state when it is mixed with other materials to produce a conductive paste, and it is easy to obtain uniform conductivity. Slurry.
例如，以導電性粉末為100質量份計，可混合0.01質量份以上且不足5質量份、理想為0.1質量份以上3質量份以下的分散劑來製備導電性粉末漿料。此外，導電性粉末漿料中的分散劑以及有機溶劑的含量可根據導電性粉末漿料的粒徑、含量等適當進行調整。另外，作為導電性粉末漿料的製造方法，無特別限定，可使用通常的混煉方法。 For example, based on 100 parts by mass of the conductive powder, a dispersant of 0.01 parts by mass or more and less than 5 parts by mass, and preferably 0.1 parts by mass or more and 3 parts by mass or less may be mixed to prepare a conductive powder slurry. In addition, the content of the dispersant and the organic solvent in the conductive powder slurry can be appropriately adjusted according to the particle diameter, content, and the like of the conductive powder slurry. The method for producing the conductive powder slurry is not particularly limited, and a general kneading method can be used.
另外，例如可以在預先將陶瓷粉末、分散劑的一部分與有機溶劑的一部分混合而製備陶瓷粉末漿料之後將剩餘的材料混合。藉此，能夠預先在陶瓷粉末上塗佈分散劑。若在陶瓷粉末表面預先塗佈有分散劑，則在與其他材料進行混合來製造導電性漿料時，陶瓷粉末亦不會凝集而維持充分地分散的狀態，容易得到均勻的導電性漿料。 In addition, for example, a part of the ceramic powder and a dispersant may be mixed with a part of the organic solvent in advance to prepare a ceramic powder slurry, and the remaining materials may be mixed. This makes it possible to apply a dispersant to the ceramic powder in advance. If a dispersant is coated on the surface of the ceramic powder in advance, the ceramic powder will not aggregate and maintain a sufficiently dispersed state when it is mixed with other materials to produce a conductive paste, and it is easy to obtain a uniform conductive paste.
例如，以陶瓷粉末為100質量份計，可混合0.01質量份以上10質量份以下、理想為0.1質量份以上5質量份以下的分散劑來製備陶瓷粉末漿料。此外，陶瓷粉末漿料中的分散劑以及有機溶劑的含量可根據陶瓷粉末的粒徑、含量等進行適當調整。另外，作為陶瓷粉末漿料的製造方法，無特別限定，可使用通常的混煉方法。 For example, based on 100 parts by mass of the ceramic powder, a dispersant of 0.01 to 10 parts by mass, and preferably 0.1 to 5 parts by mass may be mixed to prepare a ceramic powder slurry. In addition, the content of the dispersant and the organic solvent in the ceramic powder slurry can be appropriately adjusted according to the particle diameter, content, and the like of the ceramic powder. The method for producing the ceramic powder slurry is not particularly limited, and a general kneading method can be used.
此外，在製備導電性漿料時使用的導電性粉末漿料以及陶瓷粉末漿料的黏度只要為120Pa‧S以下左右，便無實際使用上之問題。導電性粉末漿料以及陶瓷粉末漿料的黏度，可根據有機溶劑的含量來進行調整。此外，作為分散劑而使用上述酸系分散劑的情況下，導電性粉末以及陶瓷粉末的分散性優異，因此在漿料黏度的調整中無須大量的有機溶劑，在製備內部電極時，能夠縮短乾燥時間，亦不易產生有機溶劑殘留等問題。 In addition, as long as the viscosity of the conductive powder slurry and the ceramic powder slurry used in preparing the conductive slurry is about 120 Pa · S or less, there is no problem in practical use. The viscosity of the conductive powder slurry and the ceramic powder slurry can be adjusted according to the content of the organic solvent. In addition, when the above-mentioned acid-based dispersant is used as a dispersant, the dispersibility of the conductive powder and the ceramic powder is excellent. Therefore, a large amount of an organic solvent is not necessary for adjusting the viscosity of the slurry, and the drying can be shortened when preparing the internal electrode. In time, it is not easy to cause problems such as residual organic solvents.
另外，亦可為，將黏合劑樹脂溶解於載體用的有機溶劑中來製備有機載體，並向漿料用的有機溶劑中添加導電性粉末、陶瓷粉末、有機載體以及分散劑，藉由混合機進行攪拌、混煉，從而製備導電性漿料。 Alternatively, an organic vehicle may be prepared by dissolving the binder resin in an organic solvent for the vehicle, and adding conductive powder, ceramic powder, an organic vehicle, and a dispersant to the organic solvent for the slurry, and using a mixer. The conductive paste is prepared by stirring and kneading.
另外，在有機溶劑中，作為載體用的有機溶劑，為了提高有機載體的親和性，理想為使用與調整導電性漿料的黏度的漿料用的有機溶劑相同的有機溶劑。載體用的有機溶劑的含量，以導電性粉末為100質量份計，例如為5質量份以上80質量份以下。另外，載體用的有機溶劑的含量，相對於導電性漿料整體，理想為10質量%以上40質量%以下。 Among organic solvents, as the organic solvent for the carrier, in order to improve the affinity of the organic carrier, it is desirable to use the same organic solvent as the organic solvent for the paste for adjusting the viscosity of the conductive paste. The content of the organic solvent for the carrier is 100 parts by mass of the conductive powder, and is, for example, 5 parts by mass or more and 80 parts by mass or less. The content of the organic solvent for the carrier is preferably 10% by mass or more and 40% by mass or less with respect to the entire conductive paste.
導電性漿料在從製造導電性漿料起經過24小時後的黏度理想為10Pa‧s以上50Pa˙s以下。 The viscosity of the conductive paste after 24 hours from the production of the conductive paste is preferably 10 Pa · s or more and 50 Pa · s or less.
另外，在印刷導電性漿料之後，乾燥得到的乾燥膜的乾燥膜密度(DFD)理想為超過5.0g/cm3，更理想為5.3g/cm3以上，進一步理想為5.5g/cm3以上，特別理想為5.6g/cm3以上。此外，乾燥膜密度(DFD)的上限無特別限定，可為6.5g/cm3以下。 In addition, after the conductive paste is printed, the dry film density (DFD) of the dried film obtained by drying is preferably more than 5.0 g / cm 3 , more preferably 5.3 g / cm 3 or more, and still more preferably 5.5 g / cm 3 or more. It is particularly preferably 5.6 g / cm 3 or more. The upper limit of the dry film density (DFD) is not particularly limited, and may be 6.5 g / cm 3 or less.
另外，藉由對導電性漿料進行網版印刷並在大氣中以120℃乾燥1小時來製備20mm見方、膜厚為1~3μm的乾燥膜時的表面粗糙度Ra(算術平均粗糙度)理想為0.04μm以下，更理想為0.03μm以下。此外，表面粗糙度Ra(算術平均粗糙度)的下限，理想為表面平坦，無特別限定，理想為超過0的值且值愈小愈好。 In addition, the surface roughness Ra (arithmetic average roughness) when preparing a dry film of 20 mm square and a film thickness of 1 to 3 μm by screen-printing the conductive paste and drying in the air at 120 ° C. for 1 hour is ideal. It is 0.04 μm or less, and more preferably 0.03 μm or less. In addition, the lower limit of the surface roughness Ra (arithmetic average roughness) is preferably a flat surface, which is not particularly limited, and is preferably a value exceeding 0 and the smaller the value, the better.
另外，上述乾燥膜的Rt(最大剖面高度)理想為0.4μm以下，更理想為0.3μm以下。此外，表面粗糙度Ra(算術平均粗糙度)的 下限理想為表面平坦，無特別限定，理想為超過0的值且值愈小愈好。 The Rt (maximum cross-sectional height) of the dry film is preferably 0.4 μm or less, and more preferably 0.3 μm or less. In addition, the lower limit of the surface roughness Ra (arithmetic average roughness) is preferably a flat surface, which is not particularly limited, and is preferably a value exceeding 0, and the smaller the value, the better.
導電性漿料能夠適宜地使用在層積陶瓷電容器等電子零件中。層積陶瓷電容器具有使用電介質生片而形成的電介質層以及使用導電性漿料而形成的內部電極層。 The conductive paste can be suitably used for electronic components such as a multilayer ceramic capacitor. A multilayer ceramic capacitor includes a dielectric layer formed using a dielectric green sheet and an internal electrode layer formed using a conductive paste.
對於層積陶瓷電容器(電子零件)而言，電介質生片中含有的電介質陶瓷粉末及導電性漿料中含有的陶瓷粉末理想為同一組成的粉末。使用本實施型態的導電性漿料製造的層疊陶瓷電容器，即使在電介質生片的厚度例如為3μm以下的情況下，亦能夠抑制片材侵蝕、生片的剝離不良。 For a multilayer ceramic capacitor (electronic component), the dielectric ceramic powder contained in the dielectric green sheet and the ceramic powder contained in the conductive paste are preferably powders of the same composition. The multilayer ceramic capacitor manufactured using the conductive paste of this embodiment can suppress sheet erosion and peeling failure of the green sheet even when the thickness of the dielectric green sheet is, for example, 3 μm or less.
[電子零件] [Electronic parts]
以下，參照圖式對本發明的電子零件等的實施型態進行說明。於圖式中，有時會適當地以示意性的方式來進行表示、變更比例尺來進行表示。另外，零件的位置、方向等，適當地參照圖1等所示的XYZ正交坐標系來進行說明。在該XYZ正交坐標系中，X方向以及Y方向為水平方向，Z方向為鉛垂方向(上下方向)。 Hereinafter, embodiments of the electronic component and the like of the present invention will be described with reference to the drawings. In the drawings, the display may be appropriately represented in a schematic manner, and the scale may be changed to be displayed. In addition, the position, direction, and the like of the parts will be described with reference to the XYZ orthogonal coordinate system shown in FIG. 1 and the like as appropriate. In this XYZ orthogonal coordinate system, the X and Y directions are horizontal, and the Z direction is vertical (up and down).
本實施型態所關於之電子零件使用上述的本實施型態的導電性漿料而形成。圖1中的A以及圖1中的B係表示作為實施型態所關於之電子零件的一個例子的層積陶瓷電容器1的圖。層積陶瓷電容器1具有電介質層12以及內部電極層11交替地層疊而成的層積體10及外部電極20。 The electronic component according to this embodiment is formed using the above-mentioned conductive paste of this embodiment. A in FIG. 1 and B in FIG. 1 are diagrams showing a multilayer ceramic capacitor 1 as an example of an electronic component related to an embodiment. The laminated ceramic capacitor 1 includes a laminated body 10 and an external electrode 20 in which dielectric layers 12 and internal electrode layers 11 are alternately laminated.
以下，對具有使用上述導電性漿料而形成的內部電極層11的層積陶瓷電容器1的製造方法進行說明。首先，在電介質生片上印刷導 電性漿料並進行乾燥而形成乾燥膜。接著，藉由壓接對在上表面具有該乾燥膜的複數個電介質層進行層疊之後，進行燒製而使其一體化，由此製備成為陶瓷電容器主體的層積陶瓷燒結體(層積體10)。之後，藉由在層積體10的兩端部形成一對外部電極20而製造層積陶瓷電容器1。以下，進行更詳細的說明。 Hereinafter, a method for manufacturing a multilayer ceramic capacitor 1 having an internal electrode layer 11 formed using the conductive paste will be described. First, a conductive paste is printed on a dielectric green sheet and dried to form a dry film. Next, a plurality of dielectric layers having the dry film on the upper surface are laminated by pressure bonding, and then fired to integrate them, thereby preparing a laminated ceramic sintered body (laminated body 10) as a ceramic capacitor body. ). Thereafter, a multilayer ceramic capacitor 1 is manufactured by forming a pair of external electrodes 20 on both ends of the multilayer body 10. Hereinafter, it will be described in more detail.
首先，準備作為未燒製的陶瓷片的電介質生片(陶瓷生片)。作為該電介質生片，例如，可列舉為將在鈦酸鋇等規定的陶瓷原料粉末中加入聚乙烯醇縮丁醛等有機黏合劑及萜品醇等溶劑而得到的電介質層用漿料在PET薄膜等支承薄膜上塗佈成片狀並進行乾燥去除溶劑而形成的生片等。此外，對由電介質生片構成的電介質層的厚度無特別限定，但以層積陶瓷電容器1的小型化的要求的觀點而言，理想為0.05μm以上3μm以下。 First, a dielectric green sheet (ceramic green sheet) is prepared as an unfired ceramic sheet. Examples of the dielectric green sheet include a dielectric layer slurry obtained by adding an organic binder such as polyvinyl butyral and a solvent such as terpineol to a predetermined ceramic raw material powder such as barium titanate in PET. A green sheet or the like formed by coating a support film such as a film into a sheet shape and drying to remove the solvent. In addition, the thickness of the dielectric layer composed of the dielectric green sheet is not particularly limited, but from the viewpoint of the demand for miniaturization of the multilayer ceramic capacitor 1, it is preferably 0.05 μm or more and 3 μm or less.
接下來，準備複數個藉由在該電介質生片的一個面上藉由網版印刷等習知的方法印刷塗佈上述導電性漿料並進行乾燥而形成有乾燥膜的片材。此外，作為導電性漿料的印刷法，可使用網版印刷以外的印刷法，可根據欲形成的電極圖案的線條寬度、厚度、生產速度等適當進行選擇。此外，印刷後的導電性漿料(乾燥膜)的厚度，從內部電極層11的薄層化的要求的觀點出發，理想為乾燥後為1μm以下。 Next, a plurality of sheets are prepared by printing-coating the conductive paste on one surface of the dielectric green sheet by a known method such as screen printing and drying the sheet to form a dried film. In addition, as a printing method of the conductive paste, a printing method other than screen printing can be used, and can be appropriately selected according to the line width, thickness, production speed, and the like of the electrode pattern to be formed. The thickness of the conductive paste (dried film) after printing is preferably 1 μm or less after drying from the viewpoint of a request for thinning the internal electrode layer 11.
接下來，從支承薄膜上將電介質生片剝離，並且以電介質生片與形成於該電介質生片的一個面上的導電性漿料(乾燥膜)交替地配置的方式進行層疊之後，藉由加熱、加壓處理而得到層積體(壓接體)。此外，亦可設為在層積體的兩面進一步配置未塗佈導電性漿料的保護用的 電介質生片的構成。 Next, the dielectric green sheet is peeled from the support film, the dielectric green sheet and the conductive paste (dry film) formed on one surface of the dielectric green sheet are alternately arranged, and then laminated, and then heated And press treatment to obtain a laminate (crimped body). In addition, a configuration in which a dielectric green sheet for protection in which a conductive paste is not applied is further disposed on both surfaces of the laminate may be employed.
接下來，將層積體切斷為規定尺寸而形成生晶片之後，對該生晶片實施脫黏合劑處理，並在還原氣體環境下進行燒製，由此製造層積陶瓷燒製體(層積體10)。此外，脫黏合劑處理中的氣體環境理想為大氣或N2氣體氣體環境。進行脫黏合劑處理時的溫度例如為200℃以上400℃以下。另外，進行脫黏合劑處理時的上述溫度的保持時間理想為0.5小時以上24小時以下。另外，為了抑制在內部電極層11中使用的金屬的氧化而在還原氣體環境下進行燒製，另外，進行層積體10的燒製時的溫度例如為1000℃以上1350℃以下，進行燒製時的溫度的保持時間例如為0.5小時以上8小時以下。 Next, the laminated body is cut to a predetermined size to form a green wafer, and then the green wafer is subjected to a de-binder treatment and fired under a reducing gas atmosphere to produce a laminated ceramic fired body (laminated Body 10). In addition, the gas environment in the debinding treatment is preferably an atmosphere or an N 2 gas gas environment. The temperature at the time of performing the debinding treatment is, for example, 200 ° C or higher and 400 ° C or lower. In addition, the holding time of the temperature at the time of performing the debinding treatment is preferably 0.5 hours or more and 24 hours or less. In addition, in order to suppress oxidation of the metal used in the internal electrode layer 11, firing is performed in a reducing gas environment, and the firing temperature of the laminated body 10 is, for example, 1000 ° C. or higher and 1350 ° C. or lower. The temperature holding time at this time is, for example, 0.5 hours or more and 8 hours or less.
藉由進行生晶片的燒製，將電介質生片中的有機黏合劑完全去除，並且對陶瓷原料粉末進行燒製而形成陶瓷製的電介質層12。另外，去除乾燥膜中的有機載體，並且使鎳粉末或以鎳作為主要成分的合金粉末燒結或熔融而一體化，從而形成內部電極層11，進而形成電介體層12與內部電極層11多層交替地層疊而成的層積陶瓷燒製體(層積體10)。此外，以將氧帶入電介質層12的內部而提高可靠性、且抑制內部電極層11的再氧化的觀點而言，可以對燒製後的層積陶瓷燒製體(層積體10)實施退火處理。 By firing the green wafer, the organic binder in the dielectric green sheet is completely removed, and the ceramic raw material powder is fired to form a ceramic dielectric layer 12. In addition, the organic carrier in the dry film is removed, and the nickel powder or alloy powder containing nickel as a main component is sintered or melted and integrated to form the internal electrode layer 11, and then the dielectric layer 12 and the internal electrode layer 11 are alternately multilayered. A laminated ceramic fired body (layered body 10) which is laminated on the ground. In addition, from the viewpoint of bringing oxygen into the dielectric layer 12 to improve reliability and suppressing re-oxidation of the internal electrode layer 11, the fired laminated ceramic fired body (layered body 10) can be implemented. Annealed.
接著，藉由對所製備的層積陶瓷燒製體(層積體10)設置一對外部電極20，由此製造層積陶瓷電容器1。例如，外部電極20具備外部電極層21以及電鍍層22。外部電極層21與內部電極層11電連接。此外，作為外部電極20的材料，例如可理想地使用銅、鎳或其等的合 金。此外，電子零件亦可使用除層積陶瓷電容器以外的電子零件。 Next, a pair of external electrodes 20 are provided to the prepared laminated ceramic fired body (layered body 10), thereby manufacturing a laminated ceramic capacitor 1. For example, the external electrode 20 includes an external electrode layer 21 and a plating layer 22. The external electrode layer 21 is electrically connected to the internal electrode layer 11. As the material of the external electrode 20, for example, copper, nickel, or an alloy thereof can be preferably used. In addition, as the electronic component, an electronic component other than a multilayer ceramic capacitor may be used.
【實施例】 [Example]
以下，基於實施例及對比例對本發明進行詳細說明，但本發明並不受實施例的任何限定。 Hereinafter, the present invention will be described in detail based on examples and comparative examples, but the present invention is not limited at all by the examples.
〔評價方法〕 [Evaluation method]
(導電性粉末漿料的分散性) (Dispersibility of conductive powder slurry)
製備由導電性粉末及分散劑以及有機溶劑構成的評價用的導電性粉末漿料，對其黏度進行測定來評價分散性。以後述的試驗1所記載的配比製備評價用的導電性粉末漿料，使用Brookfield公司製造的B型黏度計以10rpm(剪切速率=4sec-1)的條件測定製備1小時後的黏度。在導電性粉末漿料的分散性不足的情況下，導電性粉末(粉末材料)凝集而形成凝集顆粒，受該凝集顆粒的影響，導電性粉末漿料的黏度上升。因而，導電性粉末漿料的黏度愈低，則表明分散性愈優異。 A conductive powder slurry for evaluation consisting of a conductive powder, a dispersant, and an organic solvent was prepared, and the viscosity was measured to evaluate the dispersibility. The conductive powder slurry for evaluation was prepared by the mixing ratio described in Test 1 described later, and the viscosity after 1 hour was measured using a B-type viscometer manufactured by Brookfield Co., Ltd. under the conditions of 10 rpm (shear rate = 4 sec -1 ). When the dispersibility of the conductive powder slurry is insufficient, the conductive powder (powder material) aggregates to form aggregated particles, and the viscosity of the conductive powder slurry increases due to the influence of the aggregated particles. Therefore, the lower the viscosity of the conductive powder slurry, the better the dispersibility.
(陶瓷粉末漿料的分散性) (Dispersibility of ceramic powder slurry)
製備由陶瓷粉末及分散劑以及有機溶劑構成的評價用的陶瓷粉末漿料，對其黏度進行測定來評價分散性。以後述的試驗1所記載的配比製備評價用的陶瓷粉末漿料，使用Brookfield公司製造的B型黏度計以10rpm(剪切速率=4sec-1)的條件測定製備1小時後的黏度。在陶瓷粉末漿料的分散性不足的情況下，陶瓷粉末(粉末材料)凝集而形成凝集顆粒，使陶瓷粉末漿料的黏度上升。因而，陶瓷粉末漿料的黏度愈低，則表明分散性愈優異。 A ceramic powder slurry for evaluation consisting of a ceramic powder, a dispersant, and an organic solvent was prepared, and its viscosity was measured to evaluate dispersibility. The ceramic powder slurry for evaluation was prepared by the mixing ratio described in Test 1 described later, and the viscosity after 1 hour of preparation was measured using a B-type viscometer manufactured by Brookfield Co., Ltd. under the conditions of 10 rpm (shear rate = 4 sec -1 ). When the dispersibility of the ceramic powder slurry is insufficient, the ceramic powder (powder material) is aggregated to form aggregated particles, and the viscosity of the ceramic powder slurry is increased. Therefore, the lower the viscosity of the ceramic powder slurry, the better the dispersibility.
(導電性漿料的分散性：黏度) (Dispersibility of conductive paste: viscosity)
製備導電性漿料，使用Brookfield公司製造的B型黏度計以10rpm(剪切速率=4sec-1)的條件測定製備後經過24小時後的黏度。在導電性漿料的分散性不足的情況下，導電性粉末、陶瓷粉末(粉末材料)凝集而形成凝集顆粒，使導電性漿料的黏度上升。因而，導電性漿料的黏度在適合於印刷的黏度範圍內越低，則表明分散性越優異。 A conductive paste was prepared, and the viscosity after 24 hours after preparation was measured using a B-type viscometer manufactured by Brookfield under the conditions of 10 rpm (shear rate = 4sec -1 ). When the dispersibility of the conductive paste is insufficient, the conductive powder and ceramic powder (powder material) are aggregated to form aggregated particles, and the viscosity of the conductive paste is increased. Therefore, the lower the viscosity of the conductive paste within the viscosity range suitable for printing, the better the dispersibility.
(乾燥膜密度) (Dry film density)
將導電性漿料載置在PET薄膜上，利用寬度為50mm、間隙為125μm的塗佈器延伸至長度約為100mm。以120℃對得到的PET薄膜乾燥40分鐘，在形成乾燥膜之後，將該乾燥膜切割為4個2.54cm(1英寸)的見方，在將PET薄膜剝離的基礎上，對4個乾燥膜的厚度、重量分別進行測定，並計算出乾燥膜密度(平均值)。 The conductive paste was placed on a PET film and extended to a length of about 100 mm by an applicator having a width of 50 mm and a gap of 125 μm. The obtained PET film was dried at 120 ° C for 40 minutes. After the dried film was formed, the dried film was cut into four 2.54 cm (1 inch) squares. After the PET film was peeled off, the The thickness and weight were measured separately, and the dry film density (average value) was calculated.
(表面粗糙度) (Surface roughness)
將製備的導電性漿料網版印刷在2.54cm(1英寸)見方的耐熱強化玻璃上，並在大氣中在120℃下乾燥1小時，由此製備20mm見方、膜厚為1~3μm的乾燥膜。基於JIS B0601-2001的標準，對乾燥膜的表面粗糙度Ra(算術平均粗糙度)、Rt(最大剖面高度)進行測定。 The prepared conductive paste was screen-printed on a heat-resistant tempered glass of 2.54 cm (1 inch) square and dried in the air at 120 ° C. for 1 hour, thereby preparing a 20 mm square and a film thickness of 1 to 3 μm. membrane. Based on the JIS B0601-2001 standard, the surface roughness Ra (arithmetic average roughness) and Rt (maximum cross-section height) of the dried film were measured.
〔使用材料〕 〔Used materials〕
(導電性粉末) (Conductive powder)
作為導電性粉末，使用Ni粉末(SEM平均粒徑為0.2μm)。 As the conductive powder, Ni powder (average SEM particle diameter: 0.2 μm) was used.
(陶瓷粉末) (Ceramic powder)
作為陶瓷粉末，使用鈦酸鋇(BaTiO3；SEM平均粒徑為0.05μm)。 As the ceramic powder, barium titanate (BaTiO 3 ; SEM average particle diameter: 0.05 μm) was used.
(黏合劑樹脂) (Binder resin)
作為黏合劑樹脂，使用乙基纖維素樹脂以及聚乙烯醇縮丁醛樹脂(PVB樹脂)。此外，預先準備相對於黏合劑樹脂(黏合劑樹脂整體為100質量%)而在萜品醇中溶解有50質量%的乙基纖維素樹脂、50質量%的聚乙烯醇縮丁醛樹脂而成的有機載體，在製備導電性漿料時使用該有機載體。 As the binder resin, ethyl cellulose resin and polyvinyl butyral resin (PVB resin) were used. In addition, 50% by mass of ethyl cellulose resin and 50% by mass of polyvinyl butyral resin in terpineol were prepared in advance with respect to the binder resin (100% by mass of the entire binder resin). Organic vehicle, which is used when preparing conductive paste.
(分散劑) (Dispersant)
作為酸系分散劑，使用下述的酸系分散劑A~E。 As the acid-based dispersant, the following acid-based dispersants A to E were used.
酸系分散劑A、B：平均分子量分別為1500(酸系分散劑A)、800(酸系分散劑B)的以聚羧酸為主鏈的烴系接枝共聚物 Acid-based dispersants A and B: Hydrocarbon-based graft copolymers having a polycarboxylic acid as the main chain having average molecular weights of 1500 (acid-based dispersant A) and 800 (acid-based dispersant B), respectively.
酸系分散劑C、D：平均分子量分別為370(酸系分散劑C)、230(酸系分散劑D)，且具有烴基及兩個羧基的酸系分散劑 Acid-based dispersants C and D: acid-based dispersants having average molecular weights of 370 (acid-based dispersant C) and 230 (acid-based dispersant D), each having a hydrocarbon group and two carboxyl groups
酸系分散劑E：平均分子量為350，且具有直鏈烴基(非支鏈)及一個羧基的酸系分散劑(在傳統的導電性漿料中使用的酸系分散劑) Acid-based dispersant E: An acid-based dispersant having an average molecular weight of 350 and having a linear hydrocarbon group (unbranched chain) and one carboxyl group (acid-based dispersant used in conventional conductive pastes)
作為鹼系分散劑，使用以下的鹼系分散劑F、G。 As the alkali-based dispersant, the following alkali-based dispersants F and G were used.
鹼系分散劑F：聚醚胺系分散劑(聚氧乙烯月桂胺) Alkali-based dispersant F: Polyetheramine-based dispersant (polyoxyethylene laurylamine)
鹼系分散劑G：脂肪族胺系分散劑(松香胺) Alkali-based dispersant G: aliphatic amine-based dispersant (rosinamine)
(有機溶劑) (Organic solvents)
作為有機溶劑，使用萜品醇(萜烯系溶劑)。 As the organic solvent, terpineol (terpene-based solvent) was used.
(試驗1) (Experiment 1)
〔導電性粉末漿料的分散性〕 [Dispersibility of conductive powder slurry]
製備由100質量份的導電性粉末(Ni粉末)、0.2質量份的分散劑以及34質量份的有機溶劑(萜品醇)構成的評價用的導電性粉末漿料，並以上 述方法對分散性(黏度)進行評價。作為分散劑，使用酸系分散劑A~E。針對各酸系分散劑的評價結果如表1所示。 A conductive powder slurry for evaluation consisting of 100 parts by mass of a conductive powder (Ni powder), 0.2 parts by mass of a dispersant, and 34 parts by mass of an organic solvent (terpineol) was prepared, and the dispersibility was determined by the method described above. (Viscosity). As the dispersant, acid-based dispersants A to E were used. The evaluation results for each acid-based dispersant are shown in Table 1.
〔陶瓷粉末漿料的分散性〕 [Dispersibility of ceramic powder slurry]
製備由100質量份的陶瓷粉末(鈦酸鋇)、0.6質量份的分散劑以及33質量份的有機溶劑(萜品醇)構成的評價用的陶瓷粉末漿料，並以上述方法對分散性(黏度)進行評價。作為分散劑，使用酸系分散劑A~E。針對各酸系分散劑的評價結果如表1所示。 A ceramic powder slurry for evaluation composed of 100 parts by mass of ceramic powder (barium titanate), 0.6 parts by mass of a dispersant, and 33 parts by mass of an organic solvent (terpineol) was prepared, and the dispersibility ( Viscosity). As the dispersant, acid-based dispersants A to E were used. The evaluation results for each acid-based dispersant are shown in Table 1.
如表1所示，平均分子量超過500的酸系分散劑A及酸系分散劑B，與以往所使用的酸系分散劑E相比，導電性粉末漿料以及陶瓷粉末漿料的黏度較低，而顯示出良好的分散性。另一方面，可知，平均分子量為500以下的酸系分散劑C以及酸系分散劑D，與以往所使用的酸系分散劑E相比，導電性粉末漿料以及陶瓷粉末漿料的黏度較高，使導電性粉末以及陶瓷粉末分散的效果較低。 As shown in Table 1, the acidic dispersant A and the acidic dispersant B having an average molecular weight exceeding 500 have lower viscosity of the conductive powder slurry and the ceramic powder slurry than the conventional acid dispersant E. While showing good dispersibility. On the other hand, it can be seen that the acid-based dispersant C and the acid-based dispersant D having an average molecular weight of 500 or less have a higher viscosity compared to the acid-based dispersant E that has been used conventionally. High, the effect of dispersing conductive powder and ceramic powder is low.
(試驗2) (Experiment 2)
以下述的方法製備導電性漿料，更詳細地進行評價。 The conductive paste was prepared by the following method and evaluated in more detail.
〔實施例1〕 [Example 1]
相對於導電性漿料整體(100質量%)，以Ni粉末為50質量%、陶瓷粉末為3.8質量%、由乙基纖維素樹脂及聚乙烯醇縮丁醛樹脂構成的黏合劑樹脂(乙基纖維素樹脂：聚乙烯醇縮丁醛樹脂(質量比)=1：1)合計為6質量%、酸系分散劑B為0.05質量%、以及餘量由萜品醇構成的配比將上述材料混合，製備導電性漿料。以上述方法對製備的導電性漿料的分散性(黏度)、乾燥膜密度、乾燥膜的表面粗糙度進行評價。將評價結果示於表2。 Based on the entire conductive paste (100% by mass), 50% by mass of Ni powder, 3.8% by mass of ceramic powder, and a binder resin (ethyl group consisting of ethyl cellulose resin and polyvinyl butyral resin) Cellulose resin: Polyvinyl butyral resin (mass ratio) = 1: 1) A total of 6% by mass, an acid-based dispersant B is 0.05% by mass, and the balance is composed of terpineol Mix to prepare a conductive paste. The dispersibility (viscosity), dry film density, and surface roughness of the dried film of the prepared conductive paste were evaluated by the methods described above. The evaluation results are shown in Table 2.
〔實施例2~6〕 [Examples 2 to 6]
除將酸系分散劑的種類以及含量設為表2所示的量以外，按照與實施例1相同的條件製備導電性漿料。以上述方法對製備的導電性漿料的黏度、乾燥膜密度、乾燥膜的表面粗糙度進行評價。將評價結果示於表2。 A conductive paste was prepared under the same conditions as in Example 1 except that the type and content of the acid-based dispersant were the amounts shown in Table 2. The viscosity of the prepared conductive paste, the density of the dried film, and the surface roughness of the dried film were evaluated by the methods described above. The evaluation results are shown in Table 2.
〔實施例7~9〕 [Examples 7 to 9]
除作為分散劑而以表3所示的量添加有酸系分散劑B以及鹼系分散劑F以外，按照與實施例1相同的條件製備導電性漿料。以上述方法對製備的導電性漿料的黏度、乾燥膜密度、乾燥膜的表面粗糙度進行評價。將評價結果示於表3。 A conductive paste was prepared under the same conditions as in Example 1 except that the acid-based dispersant B and the alkali-based dispersant F were added as the dispersant in the amounts shown in Table 3. The viscosity of the prepared conductive paste, the density of the dried film, and the surface roughness of the dried film were evaluated by the methods described above. The evaluation results are shown in Table 3.
〔實施例10~13〕 [Examples 10 to 13]
除作為分散劑而以表4所示的量添加有除酸系分散劑B以外的鹼系分散劑F或者鹼系分散劑G以外，按照與實施例2相同的條件製備導電性漿料。以上述方法對製備的導電性漿料的黏度、乾燥膜密度、乾燥膜的表面粗糙度進行評價。將評價結果示於表4。 A conductive paste was prepared under the same conditions as in Example 2 except that as the dispersant, an alkali-based dispersant F or an alkali-based dispersant G other than the acid-based dispersant B was added in an amount shown in Table 4. The viscosity of the prepared conductive paste, the density of the dried film, and the surface roughness of the dried film were evaluated by the methods described above. The evaluation results are shown in Table 4.
〔對比例1〕 [Comparative Example 1]
除了將分散劑變更為酸系分散劑E以外，按照與實施例1相同的條件製備導電性漿料。以上述方法對製備的導電性漿料的黏度、乾燥膜密度、乾燥膜的表面粗糙度進行評價。將評價結果示於表2。 A conductive paste was prepared under the same conditions as in Example 1 except that the dispersant was changed to an acid-based dispersant E. The viscosity of the prepared conductive paste, the density of the dried film, and the surface roughness of the dried film were evaluated by the methods described above. The evaluation results are shown in Table 2.
〔對比例2〕 [Comparative Example 2]
除了將分散劑變更為酸系分散劑E以外，按照與實施例3相同的條件製備導電性漿料。以上述方法對製備的導電性漿料的黏度、乾燥膜密度、乾燥膜的表面粗糙度進行評價。將評價結果示於表2~4。 A conductive paste was prepared under the same conditions as in Example 3 except that the dispersant was changed to an acid-based dispersant E. The viscosity of the prepared conductive paste, the density of the dried film, and the surface roughness of the dried film were evaluated by the methods described above. The evaluation results are shown in Tables 2 to 4.
〔對比例3〕 [Comparative Example 3]
除了將分散劑變更為酸系分散劑C以外，按照與實施例3相同的條件製備導電性漿料。以上述方法對製備的導電性漿料的黏度、乾燥膜密度、乾燥膜的表面粗糙度進行評價。將評價結果示於表2。 A conductive paste was prepared under the same conditions as in Example 3 except that the dispersant was changed to the acid-based dispersant C. The viscosity of the prepared conductive paste, the density of the dried film, and the surface roughness of the dried film were evaluated by the methods described above. The evaluation results are shown in Table 2.
〔對比例4〕 [Comparative Example 4]
除了將分散劑變更為酸系分散劑E以外，按照與實施例2相同的條件製備導電性漿料。以上述方法對製備的導電性漿料的黏度、乾燥膜密度、乾燥膜的表面粗糙度進行評價。將評價結果示於表4。 A conductive paste was prepared under the same conditions as in Example 2 except that the dispersant was changed to an acid-based dispersant E. The viscosity of the prepared conductive paste, the density of the dried film, and the surface roughness of the dried film were evaluated by the methods described above. The evaluation results are shown in Table 4.
(評價結果) (Evaluation results)
實施例的導電性漿料，當與同在實施例中使用的酸系分散劑等量地使用酸系分散劑C、E的對比例的導電性漿料相比較的情況下，可確認導電性漿料的黏度較低而分散性優異，提高了乾燥膜密度，並且乾燥膜表面更加平滑。 When the conductive paste of the example was compared with the conductive paste of the comparative example using the acid-based dispersants C and E in the same amount as the acid-based dispersant used in the examples, the conductivity was confirmed. The viscosity of the slurry is low and the dispersibility is excellent. The density of the dried film is increased, and the surface of the dried film is smoother.
此外，本發明的技術範圍不限於上述實施型態等中說明的方式。有時會省略上述實施型態等中說明的要件中的一個以上。另外，可適當地對上述實施型態等中說明的要件進行組合。另外，只要法律允許，援引在上述實施型態等中引用的全部的文獻的公開內容而作為本文記載的一部分。 In addition, the technical scope of the present invention is not limited to the modes described in the above-mentioned embodiment and the like. In some cases, one or more of the requirements described in the above-mentioned embodiment and the like may be omitted. In addition, the elements described in the above-mentioned embodiment and the like may be appropriately combined. In addition, as long as the law permits, the disclosure content of all documents cited in the above-mentioned embodiments and the like is cited as a part of the description herein.
本發明的導電性漿料進一步提高分散性、塗佈後的乾燥膜密度以及乾燥膜表面的平滑性，特別適宜用作作為行動電話、數位設備等小型化得以發展的電子設備的晶片零件的層積陶瓷電容器的內部電極用的原料。 The conductive paste of the present invention further improves the dispersibility, the density of the dried film after coating, and the smoothness of the surface of the dried film, and is particularly suitable for use as a layer for a wafer part of an electronic device where miniaturization such as a mobile phone and a digital device has been developed Materials for internal electrodes of ceramic capacitors.
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